Process for removing copper compounds from copper-sweetened hydrocarbon oil



Patented Dec. 11, 1945 PROCESS FOR POUNDS FROM COPPER-SWEETENED HY- DROCARBON OIL Kenneth M. Brawn, Chicago, 111., assignor to Universal Oil Products Company, Chicago, 11]., a

corporation of Delaware No Drawing. Application July 24, .1943,

" Serial No. 496,043 a Y 6 Claims.

This invention relates to the treatment of hydrocarbon oil for the removal of metal compounds and other undesirable dissolved constituents, and moreparticularlyit relates to the treatment of copper-sweetened gasoline. and naphtha for the removal of copper compounds and other undesirable constituents. y I u n One of themethodsnow in use for refining hydrocarbon oil and particularly gasoline and naphtha in order t remove-deleterious sulfur compounds, is the copper sweetening method as is illustrated in R. B.-Day Patent 1,948,565. Various sweetening processes'have been suggested in which other metal salts such ascopper chloride; zine salts and particularly zinc chloride, etc., are utilized; 7'

In the copper sweetening process, it has been found that the gasoline after sweetening contains copper compounds and possibly other undesirable dissolved'constituents and that these compounds exert an undesirable color effect to the gasoline. It is an object of-the' present invention to treat the sweetened gasoline in a novel manner in order to'remove 'the'copper' compounds and other undesirable constituents from the gasoline. In a broad aspect the present invention relates to the treatment of hydrocarbon oil for the removal of metal compounds which comprises contacting said oil with a basic or sub-carbonate of the elements in the right-hand column of group II of the periodic table.

In one specific embodiment the present invention relates to a process for the removal of copper compounds from copper-sweetened gasoline which comprises treating said gasoline with basic magnesium carbonate.

According to the present invention, the coppersweetened gasoline is percolated or otherwise contacted with a treating agent comprising as its active constituent a basic or sub-carbonate of the elements in the right-hand column of group II of the periodic table. The preferred treating agent comprises basic magnesium carbonate.

The chemical formula of the basic or sub-carbonates of these elements has been fairly well established although there seems to be a slight disagreement among the various authors in cer tain instances. However, the following formulae are listed as representing their approximate chemical composition:

Magnesium basic carbonate 3 8CO3M8(OH)2'3H2O Zinc sub-carbonate 2Z11C03 3Z1'1(0H) 2 Beryllium basic carbonate V (Bo) 5002-51150; I Z

Mercury basic carbonate HQCOs' H O Although the existence of basic carbonate'of cadmium has been definitely established, its exact chemical formula'has; apparently not been accurately determined. I

It is understood that these various "treating agents are not necessarily equivalent in efiecting removal of 'meta1 compounds'and other undesirable constituentsfrom hydrocarbon oil, r I

The treating agent of the present invention is preferably utilized in the form of a bed of granular'solid contact material althoughthednvention is not limited to this. Contacting'mayflbe carried out using powders, slurries and the like. The basic or sub-carbonates of the presentinventionmay be produced by precipitation or by other well known methods and the carbonates may then be mixed with or distributed over the surface of relatively inert spacing materials or carriers such as fullers earth, bentonite clays, ground pumice, etc., in order to give better distribution and a greater surface of contact.

The operation of the process is extremely simple and consists merely in passing the coppersweetened gasoline through a bed of granular material containing the basic or sub-carbonate at atmospheric or slightly increased temperatures, using pressure, if desired, to maintain substantially liquid phase conditions. Although atmospheric temperature is usually used, moderately elevated temperatures may be employed, for example up to about F.

It has been found beneficial in certain cases to add a small but definite amount of moisture. It is believed that the moisture serves to maintain the activity of the treating agent.

The following examples are introduced for the purpose of further illustrating the present invention, but not with the intention of unduly limiting the same.

EXAMPLE I A naphtha was percolated at atmospheric temperature through a contact mass comprising cupric sulfate and ammonium chloride mixed with pumice under conditions to dissolve a high content of copper in the naphtha. According to ENT 7 comprises treating said oil with basic magnesium carbonate in solid form.

2. A process for removing copper compounds from copper-sweetened hydrocarbon oil which comprises percolating said oil through a. bed of seiid 'rnate'flal comprising lfis'ifi iilfii'g'fihifim carnarrate.

I 3. A process for removing copper compounds from copper-sweetened hydrocarbon oil which 'Tdlil' Experiments Treating agent 5% basic magnesifiincar 1%- bi'sic xii'egfiesj ufiicar 5% were rfia'gnesiumpar- 20.7% basic magnesium bonate on 95% pumice. bb'rmte on 89% pumice; bonate on 95% pum1ce+ carbonate on 79.3% pum- 2 cc. of water. ice-H cc. of water.

Amount of reagent em- 15 15 .r 30 30.

ployed in grams. Copper content of the first 1.69 1.62 1.35 1.42.

400 cc. of treated naphtha,

Mg/L.

The data reported active are mam laboratory experiments and it rs to be noted that ther is a considerable decrease in the copper content by treatment in accordance with "the present lavastion. In commercial sperm-en's employing large 9 4 2 519? het ieeti a a ent the reduction in copper will be materially increased.

Exsmrnn II A few drops oi? copper meats-1n a remade 's'olutfipiigjveie argued "to 30 of ti i e sweetened rjapht a, jIhe was stream; blue in carer; The was P cke w a 50% volume tmosph ric emperature. satisfies treatment the fr'ijaphthatva's colorless and sat'stamiaiigr 66pri re ie- 1 claim ag ng invention} 1 A process jrj i festering copper 'om'fibui ds from tagger-sweetened fivdio'iiarbdh 'oil Which ear-beasts A sofid the presence or but erreetivea annter'warer.

I characterized in that said bedcomprises a solid carrier for the magnesium compound. 

